Conversion of hydrocarbons with a hf catalyst, the reforming of the gasoline fraction and the regeneration of the hf with hydrogen from the reforming zone



Patented Feb. 23, 1954 CONVERSION OF HYDROCARBONS WE'EH A HF CATALYST, THE REFORMING OF THE GASOLINE FRACTION AND THE REGEN- ERATION OF THE HF WITH HYDROGEN FROM THE REFORMING ZQNE Louis S. Kassel, Oak Park, 111., assignor to Universal Oil Products Company, Chicago, Iii, a

corporation of Delaware Application June 30, 1950, Serial No. 171,498

17 Claims.

This invention relates to the conversion of hydrocarbons. More particularly, it is concerned With the production of motor fuel from heavy hydrocarbon oil by means of a combination cracking-reforming operation wherein hydrogen fluoride is employed as the cracking catalyst. Still more specifically, it is concerned with a method of regenerating hydrogen fluoride catalyst that has been used in the conversion of hydrocarbons.

Present day commercial catalytic cracking processes, employing refractory metal oxide catalysts, possess certain disadvantages that are exceedingly difiicult to overcome. The principal disadvantages are:

1. Less than optimum utilization of the hydrogen present in the charge stock. This is reflected in product distribution and quality, which, al-- though fairly satisfactory, nevertheless fall short of the theoretical obtainable.

2. A relatively low tolerance for charge stock contaminants, particularly metallic contaminants, which tend to deleteriously affect the activity and selectivity of the catalyst and which usually promote excessive hydrogen formation. 12

This severely limits the type of charging stocks that can be successfully processed.

I have invented a new method of catalytically converting heavier than gasoline hydrocarbon oils into motor fuels that does not possess the objectionable features listed above.

It is an object of this invention-to convert heavier-than-gasoline hydrocarbons to gasoline boiling range hydrocarbons.

It is another object of this invention to provide a catalytic cracking process that is capable of successfully handling topped crudes, reduced crudes, and similar charging stocks that normally contain appreciable quantities of contaminants.

Another object of this invention is to selective ly crack hydrocarbons in the presence of liquid hydrogen fluoride to thereby produce relatively small amounts of dry gas and relatively large amounts of saturated gasoline boiling range hydrocarbons that are particularly responsive to method of purifying hydrogen fluoride catalyst that has been used in the conversion of hydrocarbons.

In a broad aspect my invention relates to the conversion of heavier-than-gasoline hydrocarbon oil to motor fuel by cracking such an oil in the presence of a cracking catalyst comprising liquid hydrogen fluoride, reforming at least a higher boiling fraction of the thus produced gasoline boiling range hydrocarbons at conditions that result in the production of hydrogen, and utilizing at least a portion of the net hydrogen to hydrogenate and purify the used catalyst phase. In one embodiment my invention relates to a method of producing motor fuel from a hydrocarbon oil heavier than gasoline which comprises contacting said oil with a catalyst comprising hydrogen fluoride at cracking conditions, recovering substantially catalyst-free gasoline boiling range hydrocarbons from the reaction products, reforming at least a portion of said hydrocarbons under conditions that result in a net production of hydrogen, and treating at least a portion of the used catalyst with at least a portion of said hydrogen under conditions to at least partially restore the activity thereof.

In a more specific embodiment my invention relates to a process which comprises cracking a hydrocarbon oil heavier than gasoline with a catalyst comprising liquid hydrogen fluoride, thereby producing lighter hydrocarbons and catalystsoluble diluent, separating the cracking zone eiiluent into a hydrocarbon phase and a catalyst phase, removing dissolved hydrogen fluoride from the hydrocarbon phase, recovering from said hydrocarbon phase gasoline boiling range hydrocarbons and subjecting the same to catalytic reforming at conditions that result in a net production of hydrogen, contacting at least a portion of said catalyst phase with at least a portion of said hydrogen at hydrogenating conditions at which at least a portion of the catalyst-soluble diluent separates from the catalyst phase, and returning at least a portion of the resultant catalyst phase to, the cracking zone.

In another specific embodiment my invention relates to a method of regenerating a contaminated catalyst comprising hydrogen fluoride containing accumulated. catalyst-soluble diluent which comprises subjecting such a catalyst in substantially the liquid phase to the action of hydrogen at a temperature and for a time sufiicient to eifect a reaction of hydrogen with said catalyst-soluble diluent and separation of at least a portion of the resultant reaction product from 3 the hydrogen fluoride catalyst, thereby effecting a purification of said catalyst.

In another specific embodiment my invention relates to a method of regenerating a contaminated catalyst comprising hydrogen fluoride catalyst containing accumulated catalyst-soluble diluent which comprises contacting such a catalyst in substantially the liquid phase in a reaction zone with hydrogen and BF3 at a temperature and for a time sufficient to eifect a reaction of hydrogen with said catalyst-soluble diluent and thereby resolve the catalyst into a hydrogenated catalyst-soluble diluent phase and a purified hydrogen fluoride phase, recovering the purified hydrogen fluoride phase, contacting reaction vapors comprising residual hydrogen and BFs with liquid hydrogen fluoride and an aromatic hydrocarbon to thereby remove BFs from the vapors by forming a Bl s- -w-aromatic hydrocarbon complex, separating said complex from residual vapors, dissociating said complex and recovering the liberated BFs, and returning the same to said reaction zone.

My invention will be further illustrated and explained in connection with the following dehave been grouped along the bottom of the figure and the bulk of the catalyst-hydrocarbon separation steps and catalyst purification steps have been grouped along the top. For purposes of simplification, pumps, compressors and the like are not shown, but it is to be understood that these items of equipment should be installed wherever necessary in an actual process.

A topped crude is passed through line i and is joined by a stream of heavy recycle oil flowing through line 2 and the commingled streams are passed into heater 3. The temperature of the combined hydrocarbon stream is raised to such a point that, after it is commingled with recycle hydrogen fluoride catalyst, the temperature of the resulting mixture is the desired cracking temperature. The heated hydrocarbon stream is withdrawn from heater 3 through line 4, is joined by a stream of recycle hydrogen fluoride passing through line 5, and the oommingled streams are introduced into cracking reactor E. The relative amounts of hydrocarbons and hydrogen fluoride that are combined should be such that, at the temperature and pressure conditions prevailing in the cracking reactor, there is a separate liquid hydrogen fluoride phase. The catalyst oil weight ratio usually will be within the range of from about 0.721 to about 3:1.

If desired, the recycle hydrogen fluoride stream may be heated prior to introduction to the crackzone. However, it usually is preferable to heat only the hydrocarbon stream and thereby avoid the corrosion problems that frequently occur in the heating of hydrogen fluoride.

Cracking reactor 7 preferably is an insulated vessel. It is necessary for best results that the reactor be provided with mixing means or that it be constructed in such a manner that intimate contact between the hydrocarbons and the catalyst may be obtained. The temperature of the reactants in the cracking zone usually is maintained above about 150 F. and below about 600 F. The preferred temperature range is from about 200 F. to about 500 F. The pressure preferably should be such that substantially all of the catalyst and hydrocarbons are in the liquid phase.

A number of reactions take place in the crackmg reactor such as splitting of 0-6 bonds and CH bonds, isomerization, alkylation, destructive alkylation, and the like. However, the net result is the production of lower boiling hydrocarbons, particularly hydrocarbons boiling in the gasoline range, together with some normally gaseous hydrocarbons. The concentration of isobutane, isopentane, isohexane and the like usually is much higher than would be expected from equilibrium values calculated from thermodynamic data. Consequently, the normally liquid hydrocarbons boiling up to about 200 F. that are produced in the cracking zone are primarily isoparafiinic. The normally liquid hydrocarbons that boil from about 200 F. to about 400 F. are largely naphthenic. Simultaneously with the reaction that produce these hydrocarbons, there is an accompanying reaction or reactions'that produces catalyst-soluble diluent, sometimes referred to as tar or sludge. This'catalyst-soluble diluent is primarily hydrocarbon in nature and includes polyunsaturated cyclic hydrocarbons. Sulfur and nitrogen compounds that may be present in the hydrocarbon charging stock are more or less selectively extracted therefrom and appear in the catalyst-soluble diluent. Similarly, metallic contaminants that are present'in the hydrocarbon charging stock appear to be preferentially soluble in the catalyst phase.

It may at times be desirable to charge hydrogen and/or boron fluoride to thecrackingzone. Hydrogen often tends to partially suppresssludge foundation and boron fluoride frequently modifies the activity and selectivity of the hydrogen fluoride.

Reaction mixture is withdrawn from cracking reactor i through line 8 containing valve 9 and is passed to settler 10. If desired, the-stream of reaction mixture may be cooled prior to introduction in settler ill in order to reduce'the solubility of the hydrogen fluoride catalyst in the hydrocarbons. In settler H], the reaction mixture separates into an upper hydrocarbon layer containing dissolved hydrogen fluoride and a lower contaminated-catalyst phase. The hydrocarbon layer is passed through line H containing valve [2 into HF stripper 43, wherein the dissolved hydrogen fluoride is removed therefrom as an overhead product. The HF-iree hydrocarbons are withdrawn from the bottom of HF stripper l3 through'line I4 and are passed into line I5 containing valve [6 and'thence into main column ii. A portion of the HF -free hydrocarbons withdrawn from the bottom of HF stripper 13 may be passed through line i81containing valve I0 and dischargedintothe top-of HF absorber .20, which will be described in greater detail hereinafter. A part or all of the cracked hydrocarbon products may be dehydrofiuorinated to remove minor amounts of combined fluorine that may be present therein.

Main column .1! is diagrammatic and may, in actual practice, comprise more than one distillation column. Normally gaseous hydrocarbons producedin cracking reactor '2' are removed'overheadfrom column 1! through line 2| containing valve 22. Since the normally liquid hydrocarbons boiling up to about 200 F., that are produced in the cracking reaction, have good antiknock characteristics, there is littleneed for reforming the same. Consequently, only a higher boiling fraction of the gasoline hydrocarbons. suchas a 200- 400 P. fraction need be reformed. When this is done, the normally liqrld hydrocarbons boiling up to about 200 F. are withdrawn from main column I 1 through line 23 containing valve 24 and are passed directly into stabilizer 25. A 200-400 P. fraction is withdrawn from main column I! through line 26 containing valve 2'? and is passed into reformer 28. If it is desired to recover as one of the products of my process a distillate utilizable as a domestic fuel oil or diesel fuel, the same may be withdrawn from main-colun I? through line 20 containing valve 30. The quality of this material is high since it is substantially saturated and aromatic-free. Higher boiling oil may be withdrawn from column I! and discarded or recycled to the cracking reactor via line 2 containing valve 31.

Returning now to the reforming step, reformer 28 may comprise one or more adiabatic or heated beds of reforming catalysts, as well as the necessary heaters, receivers, compressors and the like. The reforming operation ordinarily will be carried out in the presence of hydrogen. Any reforming catalyst that is capable of promoting dehydrogenation of naphthenes under the reforming conditions employed may be used in the reforming step of my process. One group of suitable catalysts comprises alumina composited with an oxide of molybdenum, chromium, or vanadium.

Usually the alumina will contain from about 5 to about of the active oxide. A preferred type of reforming catalyst for use in my process comprises at least one refractory oxide composited or associated with platinum or palladium, said catalyst being capable of promoting hydrocracking of parafiins and dehydrogenation of naphthenes. A preferred type of catalyst that falls in this category are those described in U. S. Patent No. 2,479,109, issued August 16, 1949. These catalysts comprise alumina, platinum, and combined halogen, especially combined fluorine and combined chlorine. They are prepared by forming a mixture of alumina and a halogen compound, the halogen preferably being in an amount of from about 0.1% to about 2.0% by weight of said alumina on a dry basis if the halogen is fluorine, and about 01-40% by weight if the halogen is chlorine, and thereafter compositing about 0.1% to about 1.0% platinum with the mixture, and subsequently heating the composite.

Another group of reforming catalysts that may be used in the present process comprises a cracking component and a metal selected from the group consisting of platinum and palladium. The cracking component ordinarily will comprise silica and at least one other metal oxide, usually selected from the group consisting of alumina, zirconia, magnesia, and thoria. Another type of cracking component that may be used in these catalysts comprise alumina-boria composites. These catalysts are made, for example, by drying a composite of silica hydrogel and alumina hydrogel and thereafter incorporating into the dry composite a metal selected from the group consisting of platinum and palladium in an amount of from about 0.1% to about 1.0%. Further details concerning the preparation of catalysts of this type may be found in U. 8. Patent No. 2,478,916, issued August 16, 1949.

Hydrocarbon reforming operations carried out in accordance with my invention ordinarily will be conducted at temperatures of from about 600 F. to about 1000 F. if the catalyst comprises a cracking component and a metal selected from the group consisting of platinum and palladium. If the catalyst comprises platinum-alumina-comlie within the range of from about 750 F. to about 1000 F.

The pressures at which my reforming step will be conducted will lie within the range of from about 0 to 1200 p. s. i. g., a total pressure of at least 250 pounds ordinarily is preferred. The weight hourly space velocity, defined as the weight of hydrocarbons charged per hour per weight of catalyst in the reaction zone, should lie within the range of from about 0.2 to about 40. The amount of hydrogen charged along with the hydrocarbons usually will be from about 0.5 to about 15 mols per mol of hydrocarbon.

Under the conditions of operation outlined above and with a charging stock that contains an appreciable proportion of naphthenes, there will be a relatively large net production of hydrogen. At least a portion of this net hydrogen will be used in the purification of the hydrogen fluoride catalyst in a manner to be described hereinafter.

The reformate produced in reformer 28 is passed through line 32 containing valve 33 and is discharged into stabilizer 35. Gaseous hydrocarbons are removed overhead through line 34 containing valve 35 and are discharged into line 2!. Stabilized gasoline, comprising the highly isoparafilnic material boiling up to 200 F. that was introduced into stabilizer through line 23 and the highly aromatic reformate, is withdrawn from stabilizer 25 through line 36. The bulk of the gasoline is passed through line 31 containing valve and is sent to storage. A portion of this gasoline, or, a fraction thereof that is more concentrated in aromatics and that is produced by distillation in equipment not shown in the diagram, is passed through line 39 containing valve 40 and is discharged into the top of catalyst hydro reactor 4|.

Used hydrogen fluoride catalyst phase from settler I0 is withdrawn through line 42 containing valve 43 and is discharged into an intermediate point in catalyst hydro reactor 41. Hydrogen, containing BF3, and prepared in a manner hereinafter described, is charged through line 44 to a low point in catalyst hydro reactor 02.

Catalyst hydro reactor 4| preferably is a counter-current contaotor in which downwardly descending liquid catalyst phase is contacted with upwardly flowing gaseous hydrogen and BFs. The temperature usually will be within the range of from about 200 F. to about 600 F. and the pressure will be such that the bulk of the catalyst will be in the liquid phase. Under the conditions maintained, hydrogen absorption will occur due to hydrogenation of at least a portion of the catalyst-soluble diluent contained inthe hydrogen fluoride catalyst phase. As a result oi this hydrogenation, the catalyst phase will resolve into a hydrocarbon phase and a more purifled hydrogen fluoride phase. It is preferred to charge boron fluoride along with the hydrogen in. order to promote the hydrogenation reaction. Reaction gases comprising primarily hydrogen and boron fluoride flowing upwardly in the upper portion of catalyst hydro reactor ii are contacted with the aromatic hydrocarbons introduced to the top portion of reactor 4! via line and with liquid hydrogen fluoride-containing additional aromatic hydrocarbons, charged to the upper portion of hydro reactor ll via line 05. The upper section of vessel M is maintained at a lower portion in order to promote formation of a apo ee 7 hit-Head ear h drocarbon m lex- T is Fema s is alable tith h dro flui id phase and 'is withdrawn with the liquid hydrogen duo: rid as u d e eser n. hase m h tom of catalyst hydro reactor 4!.

The combined'hydrocarbon and acid phases are. Withdrawn from thehottom of reactor ii thro h line 45 containing valve 41 and are intf-pqueed into settler 48, wherein a separation into an upperhydrocarbon phase and a lower hydrogenfluoride phase is effected. The hydroa e i are is withdrawn h u line is @011- tai frig valve 59 and is passed to HF stripper 53. The hydrogen fluoride phase, containing dis solved BF-g l lil-aromatic hydrocarbon complex, at? se le i thd a n ou h e it remainin 5 and s. di ar into the top of 13F; stripper 53 Hydrogen from the re- 1 mg unit is introduced into the lower port of- Blfz stripper 5;} via line 54 containing W14??? Th? E -HF '?1 Q h r a n complex is decomposed in stripper 53. The overhead from this, stripper omprises. a migture of hydrogen and BFs and is passed through line Al cpiitainh'igvalve into the lower portion ofcatalyst hydro reactor 41. iThe liquid bottoms product in BF; stripper 53 is withdrawn through line 51 containing valve 53 and introduced into settler 59. An upper hydrocarbon phase com prising aromatics separates from the lower phase comprisin hydrogen fluoride in settler 59, becausethe aromatic hydrocarbons are less soluble in. the hydrogen fluoride in the absence of the 353. The, aromatic hydrocarbon layer containing. dissolved hydrogen fluoride is withdrawn through line 68; containing valve 6i and discharged; into line 45. Hydrogen fluoridephase is Withdrawn from settler. 59 through line 62 containing valve 83. A portion of the hydrogen fluoride phase is passed through line 4,5 containing valve 54 and is discharged. into the top of catalyst hydro reactor 41. The remainder of the hydrogen fluoride is passed into line 65 and the bulk thereof is, passed into line 66 containing valve El and is discharged into line Sand recycled J to. the cracking reactor.

Since the. hydrogen fluoride phase that is withdrawn from settler 59 still contains a small amount of catalyst-soluble diluent or sludge, a portion of said hydrogen fluoride phase preferably is passed through line 68 containing valve 69 intoI-IF regeneration column 10. This column comprises a flash distillation or fractional distillation zone and substantially-pure: hydrogen fluoride is removed overhead via line 5. and is recycled to the cracking reactor. Sludge, comprising hydrocarbons, metallic impurities, sulfur compounds, nitrogen compounds, and the like, are, withdrawn from the HF regeneration column through linev ll containing valve '52 and are withdrawn from the process. The HF regeneration column may be operated in such a manner that the bulk ofthe water in the hydrogen fluoride phase charged to the column is removed together with the sludge. Thus said regeneration column may actv as a drying or dehydration column to removefrom the acid phase water that is picked up by said acid phase from the. hydrocarbons charged to. the hydrocracking reactor.

l.=l',etu'rning n w; to' catalyst hydro reactor 41, the gas leaving the top oi said reactor will contain some hydrogen fluoride, consequently it is Pass d hy-sushi 1 a "J nn ngs v and is discharged into' the lower portion of HF- absorber ZQ'Wliereiii it is ctm aea wasns free hydrocarbons from P?- stripper l3. Hydrocare bons containing dissolved hydrogen fluoride are withdrawn from the bottom of HF absorber 20 through line '15 containing valve it and are passed into HF stripper E3. The vaporous over head material withdrawn from HF stripper 13 is passed through line ll containing valve '18, is passed through condenser 19 and is discharged into receiver 38. Noncondensed gases, containing some hydrogen fluoride, are withdrawn through line 3! containing valve 82 and are introduced into HF absorber 2 8 to remove the hydrogen fiuoride from said gases. Substantially HF-free gases exiting from the top of HF absorber 2b are withdrawn through line 83 containing valve 3 3 and are discharged into line 2| or returned to the reforming system. The liquid present in receiver 8B is withdrawn through line {25 containing valve 86 and discharged into settler $3, wherein a separation is effected into a hydrocarbon layer and a hydrogen fluoride layer. The hydrocarbon layer is withdrawn through line 88 containing valve 89 and is discharged into the top of HF stripper l3 as reflux therefor. The hydrogen fluoride phase present in settler 81 is withdrawn through line 9% containing valve 9i and is discharged into line 52 and is passed into catalyst hydro reactor M.

The process herein described is able to achieve outstanding results in product distribution and product quality because it solves two major. problems that have heretofore prevented such results, namely, hydrogen balance and charge stock contamination. The problem of hydrogen balance may be illustrated by studying the come position of hi h quality gasoline and distillate. the two major products of my process. The following blend is an excellent gasoline, and is representative of the type that is produced in my process.

Component Formula Mole Isobutcne 041- .076i entanc 05H 1320 Iso ioxaues. CsHu i320 Benzene l Cells 1320 Toluene CzH 1319 Xylenes. GSI'IIO 1319 'I-rirneth 1 scene. C l-l .1319 Tetramethylbenzencs O l-l .13i9

vidual components is from 13.13 weight percent,

for decalin or bicyclopentane to 15.60 weight per cent for decanes.

In hydrocarbon conversion processes forthe formation of motor fuel from higher boiling hydrocarbons there will always be at least some slight gas formation. In the present process the gas is predominantly propane. A reasonable overall product composition is This value of 12.65 weight per cent is approximately the hydrogen content of the reduced crude fraction of a typical Mid-Continent crude. Thus it can be seen that if the gas formation is held down to a reasonable value and if the h drogen is distributed in the correct proportions between the gasoline and the distillate, excellent results can be obtained. I obtain the required hydrogen proportionation by producing primarily isoparafiins and naphthenes in' the cracking reaction, dehydrogenating the gasoline boiling range naphthenes in my reforming step. and hydrogenating the catalyst phase with the resultant net production of hydrogen to thereby form distillate having the desired hydrogen content. Consequently, it can be seen that by means of my integrated combination process I am able to achieve results that have not heretofore been obtained.

The harmful effect of gas formation may be seen from the following'caloulation. The gasoline plus distillate, in the proportions produced in my process, contains 12.35 weight per cent hydrogen. the expense of this liquid product. If excess hydrogen in the excess gas is compensated by supply of external hydrogen (for example, by reforming a straight run gasoline fraction in admixture with the gasoline from the cracking reactor), then 1 weight per cent propane formation requires 0.0679 weight per cent external hydrogen, or 38.7 cubic feet per barrel, and reduces the yield of liquid products by 0.93 weight per cent. Similarly, 1 weight per cent methane formation requires 0.146 weight per cent external hydrogen, or 83 cubic feet per barrel, and reduces the yield of liquid product by 0.85 weight per cent. If excess hydrogen in the excess gas is compensated by elimination .of a hydrogen poor product from the system, the yield of desired liquid products is affected far more drastically. Whether the hydrogen poor product is tar withdrawn from the HF regeneration column in my process, or coke burnt in the regenerator of a fluid catalytic cracking unit, it will contain at least 7.75 weight per cent hydrogen, corresponding to (OH) .r. Then 1 weight per cent of propane formation is associated with 1.9 weight per cent of (CHM, and 2.29 weight per cent loss in desired products. And 1 weight per cent of methane involves 2.78 weight per centof (CI-Dr, 3.78 weight per cent loss of desired products. A third way in which hydrogen waste in a gas can be compensated is by robbing the distillate fuel fraction, with a consequent drastic loss of quality. All refining schemes for producing motor fuel from higher boiling hydrocarbons that are built around catalytic cracking and/or hydrocracking waste hydrogen gas, and therefore suffer one or more of the following effects:

1. Poor yield of desired products 2. Poor quality of distillate fuel 3. Excessive external hydrogen consumption Excess gas production must be at As indicated above, careful hydrogen management permits my process to be operated on Mid- Continent reduced crude with little or no external hydrogen supplied. in the case of more aromatic charge stocks, hydrogen contents may be as low as about 11.2 weight per cent corresponding to a hydrogen deficiency or about 800 cubic feet per barrel. Fortunately, the straight run gasoline from such crudes frequently gives hydrogen yields on reforming in the range 800- 1200 cubic feet per barrel. of this type will thus have a high enough ratio of straight run to reduced crude to yield an overall hydrogen balance, if the straight run gasoline is charged to my reforming step. There are a few very heavy aromatic crudes that are so deficient in hydrogen that it will be necessary to use external hydrogen therewith in order to remain in hydrogen balance.

From the foregoing discussion, it can be seen that one of the advantageous embodiments of my invention comprises charging an entire crude oil to my main column ll, sending to the cracking reactor heavy virgin oil and heavy recycle 1 oil, withdrawing distillate fuel oils as desired and sending to a reforming zone gasoline produced in the cracking reaction together with straight-run gasoline. Thus, my process provides a method for refining an entire crude oil in one integrated operation.

It can be further seen that it is necessary for high yields of desired products to hydrogenate L in conventional cracking processes, which cannot successfully handle residual stocks, but only selected fractions of the crude.

4. Gives good results with feed stocks, e. g., stocks containing metallic contaminants, that cannot be satisfactorily handled in present commercial catalytic cracking processes.

5. Uses a cracking catalyst that is continuously regeneratable.

6. Is economical with respect to heat, since there is no major vaporization step in the cracking and catalyst purification portions of the process.

I claim as my invention:

l. The method of producing motor fuel from a hydrocarbon oil heavier than gasoline which comprises contacting said oil with a catalyst comprising hydrogen fluoride at cracking conditions, recovering substantially catalyst-free gasoline boiling range hydrocarbons from the reaction products, reforming at least a portion of said hydrocarbons under conditions that result in a net production of hydrogen, and treating I at least a portion of the used catalyst with at least a portion of said hydrogen under condi- V tions to at least partially restore the activity 1 thereof.

2. The method of producing motor fuel from a hydrocarbon oil heavier than gasoline which comprises contacting said oil with a catalyst comprising hydrogen fluoride at a cracking tem- The lighter crudes perature and for a time sufficient to effect crackme and under a pressure sufficient to maintain.

the hydrogen fluoride and hydrocarbon oil substantially in the liquid phase, recovering substantially catalyst-free gasoline boiling range hydrocarbons from the reaction product, reforming at least a portion of said hydrocarbons under conditions that result in a net production of hydrogen, and treating at least a portion of the used catalyst with at least a portion of said hydrogen under hydrogenating conditions to at least partially restore the activity thereof.

3. The method of cracking hydrocarbons which comprises subjecting a heavy hydrocarbon to the action of a catalyst phase comprising hydrogen fluoride at cracking conditions to thereby produce lighter hydrocarbons and catalyst-soluble diluent, separating the cracking zone efiluent into a hydrocarbon phase and a catalyst phase, recovering gasoline boiling range hydrocarbons from said hydrocarbon phase, subjecting at least a portion of the gasoline boiling range'hydrocarbons to catalytic reforming .that results in a net production of hydrogen, treating at least a portion of the separated used catalyst phase with at least a portion of said hydrogen at conditions'at which there is consumption of hydrogen and separation of at least a portion of the catalyst-soluble diluent from the catalyst phase, and returning at least a portion of the resultant catalyst phase to the cracking zone.

4."Ihe process which comprises cracking a hydrocarbon oil heavier than gasoline with a catalyst comprising liquid hydrogen fluoride, thereby producing lighter hydrocarbons and catalyst-soluble diluent, separating the cracking zone eilluent into a hydrocarbon phase and a catalyst phase, removing dissolved hydrogen fluoride from the hydrocarbon products, recovering from the hydrocarbon products gasoline boil- 4- ing range hydrocarbons and subjecting the same to catalytic reforming at conditions that result in a net production of hydrogen, contacting at east a portion of said catalyst phase with at least a portion of said hydrogen at hydrogenating conditions at which at least a portion of the' catalyst-soluble diluent separates from the cata-' ly'st phase, and returning at least a portion of the resultant catalyst phase to the cracking zone.

5. The process of claim 4 further characterized inthat the hydrogenation of the catalyst phase in that the catalytic reforming step is conducted in the presence of hydrogen and a catalyst comprising about (Ll-1.0% platinum and about 0.1- 4.0% combined chlorine on alumina.

9. The process which comprises cracking a hydrocarbon oil heavier than gasoline with a catalyst comprising liquid hydrogen fluoride, thereby producing lighter hydrocarbons and catalyst-soluble diluent, separating the cracking Zone effluent into a hydrocarbon phase and .a

catalyst phase, removing dissolved. hydrogen.

fluoride from the hydrocarbon products; recovering' from the hydrocarbon products gasoline"- boiling range hydrocarbonsand subjecting the same to catalytic reforming at conditions that result in the net production of hydrogen, contacting at least a portion of said catalyst phase with at least a portion of said hydrogen at hydrogenating conditions at which at least a portion of the catalyst-soluble diluent separates from the catalyst phase, returning a portion of the resultant catalyst phase to the cracking zone, distilling another portion of the catalyst phase to re-' move residual catalyst-soluble diluent therefrom, and returning the distilled hydrogen fluoride-to.

the cracking zone.

10. The 'processwhich comprises crackingqa hydrocarbon: oil heavier than. gasoline witha catalyst comprising liquid hydrogen fluoride, lighter 1 hydrocarbons. andcatalyst-soluble diluent, separatingthe cracking-1,

thereby producing zone' efiiuent into a hydrocarbon phase and a catalyst phase, removing dissolved hydrogen. fluoride from the hydrocarbon products, recov.- a ering from the. hydrocarbon products gasoline... boiling range hydrocarbons-and at least one heavier-than-gasoline. fraction, subjecting. at. least a portion of the gasoline boiling range hydrocarbons-to catalytic reformingat; COHdl-w tions that result in a netproductionoi hydro-.

gen, contacting at least a portion of said catalyst.

phase with at least a portion of said hydrogen at hydrogenatingconditions at-which at. leastcaa.

carbon phase in a stripping; zone,v-..recovering...

gasoline boiling-=rangehydrocarbons from the. stripped hydrocarbon phase andsubjecting: at least a portion of the gasoline boiling range hy-.-, drocarbonsto catalytic reforming at conditions.v that result in the production of Y hydrogen, pars. tially purifying theHF phase by. subj acting. the same to the'action of: at least a portion .ofsaid hydrogen and boron fluoride atconditions that. result in hydrogen absorptionand separation. of. hydrocarbons from the HF. phase, recoveringsaid separated hydrocarbons and strippingdissolved HF therefrom, recycling the bulk of. the purified HF to thecracking step, distilling aportion of-.. the'purified HF to further purify .the same,-and returning the further purified HF to-thecracking. zone. 1

12. The method of: regenerating .a contaminated-catalyst comprising-hydrogen fluorideicona taining, accumulated catalyst-soluble diluent Y, which comprises contacting such a catalyst in" substantially liquid phase in. a reaction zone.-with.. hydrogen and-boron fluorideat a temperatureanda for a timesuflicienttotefiect a reaction of hydro-: gen with said catalyst-soluble diluent and thereby resolve :the catalyst into "a hydrogenated 1 catalyst-soluble diluent phase: and a purified hy-'-'-- drogen fluoride phase, recovering the purified-hysdrogen fluoride phase, contacting reaction vapors. comprising residuaLhydrogen and boron fluoride; with liquid hydrogen fluoride and anfaromatict hydrocarbon to thereby remove'boron'fiuoride 13 from the vapors by forming a BFa-HF-aromatic hydrocarbon complex, separating said complex from residual vapors, dissociating said complex, recovcringthe liberated BFs and returning the same to said reaction zone.

13. The process which comprises cracking a heavier-than-gasoline oil with liquid hydrogen fluoride catalyst to produce gasoline and catalystsoluble diluent, separating the reaction mixture into a hydrocarbon phase and an HP phase, removing dissolved I-lF from the hydrocarbon phase, recovering gasoline boiling range hydrocarbons from the HF-free hydrocarbon phase and subjecting at least a part of said gasoline boiling range hydrocarbons to catalytic reforming at conditions that result in a net production of hydrogen and aromatic hydrocarbons, charging the used liquid hydrogen fluoride catalyst to an intermediate point in a hydrogenation zone, charging hydrogen and boron fluoride to a lower point in said zone, maintaining the temperature and time of contact in said zone sufificient to hydrogenate at least a portion of the catalystsoluble diluent and thereby resolve the catalyst into a hydrocarbon phase and a purified hydrogen fluoride phase, charging an aromatic hydrocarbon-containing fraction of the reformate together with liquid hydrogen fluoride to an upper portion of said zone and therein countercurrently contacting the same with reaction vapors to thereby remove BFs from the vapors by forming a BFs-HF-aromatic hydrocarbon complex, withdrawing substantially BF'z-free vapors as an overhead product from said zone and recovering hydrogen fluoride therefrom, withdrawing a mixture of hydrocarbon phase, purified hydrogen fluoride phase, and the BFz-I-lF-arornatic hydrocarbon complex as a bottoms product, separating the hydrocarbon phase therefrom, removing dissolved HZF from said hydrocarbon phase, charging the purified hydrogen fluoride phase containing the bulk of the BFa-HF-aromatic hydrocarbon complex to the upper portion of a stripping zone and hydrogen from the reforming step to the lower portion and therein stripping BF: from the hydrogen fluoride phase and causing aromatic hydrocarbons to separate from said phase, passing efiiuent hydrogen containing BR; and liberated aromatic hydrocarbons to the hydrogenation zone, recycling a portion of the hydrogen fluoride phase to the cracking step, distilling another portion to remove residual contaminants therefrom, and recycling the thus purifled hydrogen fluoride to the cracking step.

14. A process which comprises cracking a heavier-than-gasoline oil with liquid hydrogen fluoride catalyst to produce gasoline and catalystsoluble diluent, separating the reaction mixture into a hydrocarbon phase and an HF phase, passing the hydrocarbon phase to an HF stripper and therein removing dissovled HF from said hydrocarbon phase, recovering gasoline boiling range hydrocarbons from the HF-free hydrocarbon phase and subjecting at least a higher boiling portion of said gasoline boiling range 6 hydrocarbons to catalytic reforming at conditions that result in the production of hydrogen and aromatic hydrocarbons, charging used liquid hydrogen fluoride catalyst to an intermediate point in a hydrogenation zone, charg- 14 phase and a purified hydrogen fluoride phase, charging aromatic hydrocarbons produced in the reforming step to the upper portion of said zone, simultaneously charging liquid hydrogen fluoride to the upper portion of said zone, contacting reaction vapors comprising boron fluoride, hydrogen, and hydrocarbon gases with thearomatic hydrocarbons and liquid hydrogen fluoride to thereby remove boron fluoride from said reaction vapors by forming a BF3-HF-aromatic hydrocarbon complex, withdrawing substantially BFafree vapors as an overhead product from said zone and charging the same to a low point in an absorber, charging a portion of the HF-free hydrocarbons from the aforementioned I-F stripper to the top of said absorber and therein countercurrently contacting the same with said gases to thereby remove hydrogen fluoride from the same, returning the liquid hydrocarbons containing hydrogen fluoride to said HF stripper, withdrawing a mixture of hydrocarbon phase, purified hydrogen fluoride phase, and BEa-I-lF-aromatic hydrocarbon complex as a bottoms product from the hydrogenation zone and separating the hydrocarbon phase therefrom, charging said hydrocarbon phase to said aforementioned HF stripper to remove dissolved HF therefrom, charging the purified hydrogen fluoride phase containing the bulk of the BFs-HF-aromatic hydrocarbon complex to the upper portion of a BFa stripping zone and hydrogen from the reforming step to the lower portion and therein stripping 131% from the hydrogen fluoride phase and caus ing aromatic hydrocarbons to separate from said phase, passing efiluent hydrogen containing BFa to the hydrogenation zone, withdrawing a liquid bottoms product from the 31% stripper and separating said eilluent into an aromatic hydrocarbon layer and a hydrogen fluoride phase, charging the aromatic hydrocarbon layer to the hydrogenation reactor, recycling a portion of the hydrogen fluoride phase to the cracking step, distilling another portion of said hydrogen fluoride phase to remove residual contaminants therefrom, recycling the thus purified hydrogen fluoride to the cracking step, passing the vaporous overhead material from the aforementioned HF stripper through a condenser and thence into a separation zone, removing gaseous material overhead from said separation zone and recycling the same to the bottom portion of the aforementioned absorber, passing the liquid in said separation zone to a settler and therein separating the same into a hydrocarbon phase and an HF phase, refluxing said 1-H stripper with said hydrocarbon phase, and recovering said HF phase for further use in the process.

15. A process which comprises fractionating a gasoline-containing oil and separating therefrom a light fraction containing gasoline hydrocarbons and a heavier fraction composed of hydrocarbons boiling above the gasoline range, subjecting at least a portion of the heavier fraction to the action of a liquid catalyst comprising hydrogen fluoride at cracking conditions, thereby producing lighter hydrocarbons and catalyst-soluble diluent, separating the cracking zone effluent into a hydrocarbon phase and a catalyst phase, removing dissovled hydrogen fluoride from the hydrocarbon products, recovering from the hydrocarbon products gasoline boiling range hydrocarbons and at least one heavier-than-gasoline fraction, subjecting at least a portion of the gasoline boiling range hydrocarbons and said light fraction containing gasoline hydrocarbons to catalytic reagemsao torming at conditions ithatresultrin a net producti'onsof hydrogen, contacting at least. a portion of said catalyst phase with at least a portion of said hydrogen at hydrogenating'condioions "at which at least a portion of the catalyst-soluble diluent separates from the catalyst phase, returning .at'least auportion of the resultant-catalystp'hase to thecracking zone, and :returning at least a :portion of said heavier-than-gasoline fraction vto the cracking zone.

516. :The method of claim 1 further character- :ized in thatsaidnil heavier than gasolineiis con- :ftactedwith said catalyst. in thepresence of boron 'fiuoride.

17. The methodiof claim *1 further :character- -ized;in that said nil :heavier than gasoline isz'con- '16 tested with *said catalystinithe' presencedf boron fluoride and/hydrogen.

LOUIS S. KASSEL.

References Cited in the file of thispatent UNITED STATES PATENTS Number Name Date 2,304,183 Layng et a1. Dec. 8, 1942 2,392,749 Lewis et a1.. Jan. '8, 1946 2,446,998 Burk Aug.'17, I948 2,448,015 Burk Aug. .31, 1948 2,479,110 Haensel Aug. '16, '1949 2,501,023 Brandt :et a1. Mar.'21, .1950 2,525,814 Radford Oct.17, 1950 

1. THE METHOD OF PRODUCING MOTOR FUEL FROM A HYDROCARBON OIL HEAVIER THAN GASOLINE WHICH COMPRISES CONTACTING SAID OIL WITH A CATALYST COMPRISING HYDROGEN FLUORIDE AT CRACKING CONDITIONS, RECOVERING SUBSTANTIALLY CATALYST-FREE GASOLINE BOILING RANGE HYDROCARBON FROM THE REACTION PRODUCTS, REFORMING AT LEAST A PORTION OF SAID HYDROCARBONS UNDER CONDITIONS THAT RESULT IN A NET PRODUCTION OF HYDROGEN, AND TREATING AT LEAST A PORTION OF THE USED CATALYST WITH AT LEAST A PORTION OF SAID HYDROGEN UNDER CONDITIONS TO AT LEAST PARTIALLY RESTORE THE ACTIVITY THEREOF. 